Impregnating and plastizing composition



May 11, 1943. R GAYLOR 2,318,684

IMPREGNATING AND PLASTICIZING COMPOSITION Original Filed Jan. 11, 1954 GENERATOR AcIDIFIEZ VESSEL ELEcTzbv/z --0 77.0072 INATOR 50 28 GAS W MATERIAL /NL E T FLUOFIIVR ED 'PPOTUCT v Patented May 11, 1943 IMPREGNATING AND PLASTICIZDIG COMPOSITION Peter J. Gaylor, Union, N. 3., assignor to Standard Oil Development Company, a corporation of Delaware rename (cries-287) This invention deals with the preparation and use of relatively high boiling oils and solids containing fluorine. It especially involves the production of fluoro derivatives boiling above 200 C.

The present application is a division of my copending application Serial No. 706,230 filed on January 11, 1934, now Patent 2,186,916, issued January 9, 1940.

In the drawing is shown in diagrammatic form an apparatus for producing fluorine-containing oils.

Heretofore chlorine derivatives have been used to a large extent for various purposes, as for example, -non-infiammable impregnating agents, plasticizers, etc., without very much success. This is due mainly to the fact that aliphatic chlorine compounds are too unstable, especially in the presence of moisture and metals, giving off hydrochloric acid very readily, and often polymerizing to dark colored heavy products. The pure aromatic chloro derivatives, such as chlorinated diphenyls or naphthalenes, have been found to be quite stable at ordinary tempera tures, but one of the main objections of such compounds is the fact that the chlorine afiects the boiling point too markedly, so that if, for example, a really non-inflammable material is desired, the amount of chlorine required to give this effect would produce only solid products having very limited uses.

Fluorine compounds are much more stable than the corresponding chlorine derivatives, makbonization of mineral oils, coal, lignite, and the like, animal, vegetable, and fish oils and other glycerides, high boiling esters such as dibutyl phthalate, tricresyl phosphate, chlorinated esters, and. other esters as those described in my U. S. Patent 2,104,408, Other compounds-which may be so treated are chlorinated petroleum products, oxidation products of oils and waxes, sulfur containing compounds, high boiling alcohols, acids, ketones, amines, amides, aldehydes, ethers, heterocyclic compounds such as pyridine, thiophene, etc., aromatic compounds or coal tar products as naphthalene, diphenyl, benzene, toluene, xylene, diphenyl oxide, diphenylene oxide, and the like, chlorinated compounds such as chlorinated or brominated wax, chlorinated naphthalene, di-

chlorethyl ether, chlor-diphenyl, brombenzene nitro compounds such as nitrobenzene, hexyl nitrate, cyclic compounds such as cyclohexane, tetralin, hexalin, dioxan, and the like, phenols, aniline and similar compounds, polymers such as polymerized isobutylene of 1,000 to 10,000 molecular weight, polystyrene, polyindene, polyvinyl acetylene, polychlorprene, and other polyvinyl compounds, or oxygenated polymers such as those described in my U. 8. Patent 2,123,641, as well as hydro rubber, rubber, chlorinated rubber,

. wax, petrolatum, thickened glycerides or voltolized mineral or glyceride oils, or stabilized esters such as those mentioned in U..S. Patent 2,107,316,

in the names of Peter J. Wiezevich and Luther ing it possible to utilize aliphatic compounds for purposes hitherto considered impractical with chlorinated products. Furthermore, in the case of aromatic hydrocarbons, for a given boiling point of the product, it is possible to introduce a considerably higher percentage of fluorine than chlorine, giving a much wider range of liquid and solid non-inflammable compounds for selection. Other advantages will be apparent from the subsequent description.

As raw materials for this process I employ organic substances, generally those capable of giving fluoro derivatives boiling above 400 F. and preferably those organic compounds boiling above 400 F. Such compounds as petroleum distillates, as for example kerosene, gas oil, lubricating oil, fuel oil, or cracking coil tar fractions,

B. Turner, aromatic materials similar to those described in my U. S. Patent 2,079,783, cellulose esters and ethers, resins such as the Bakelite, coumarone, and other types, rosin, shellac, plastics, products obtained by the action of the silent electric discharge, asphalts, and the like.

In general, the fluoro derivatives may be prepared by treating the raw material with fluorine which may be conveniently obtained by electrolysis of a metallic fluoride such as CaFz, KF, KFHF, and the like, or for example by methods such as those described in my '0'. S. Patent 2,090,772.

A method which may be used to advantage is shown in the drawing. Numeral l is a generator for the production of hydrogen fluoride, equipped with stirrer 2 and suitable means of heating. These may be constructed of copper, iron coated with lead, resistant plastic, or other suitable corrosion resistant material. Sulfuric acid and calcium fluoride used for the production of the hydrogen fluoride may be introduced into the generator at '3, and the sludge formed drawn oil at 5, while hydrogen fluoride vapor is led out at 4 directly to a scrubber 8, or through line 34 for indirect fluorination of chloro compounds as will be explained later. Scrubber 6, constructed of resistant metal or plastic is equipped with baffles or plates, 1, upon which may be circulated a purifying solution such as a solution of fuming sulfuric acid containing 2-l0% potassium dichromate. This mixture is well suited'to remove sulfur dioxide and other impurities from the vapor. The solution is collected in corrosion resistant vessel- 9 and circulated by pump IIIv through line H into chamber 0, and may be redouble salt KEHF which is removed at 16. Any

unused HF may be recirculated by forcing it through line l1.

The double salt KFI-IE (I9) is then electrolyzed in a copper electrolyzer l8 equipped with carbon electrodes 20 and suitable insulating caps 2| made of fluorspar or the like, and heated by some suitable means. It is preferable to keep the temperature at 200-350 C. in the electrolyzer, so that by a current or 10-20 amperes at about volts, a reasonably steady stream of fluorine may be maintained at 22 and drawn oif to storage through line 35, or led directly into fluorinator 26. Hydrogen will be liberated at 25. and may be collected in a suitable reservoir. The pressure on both sides 01' the V of the electrolyzer must be kept at the same value as closely as is practical. since otherwise th fluorine or hydrogen would mix. e

The fluorine so formed is led by pipe 22 into fluorinator 26 equipped with jacket 30 and inner coil 21 capable of cooling or heating the contents 33, while they are stirred with stirrer 32. The material to be fluorinated, such as mineral or vegetable oil, naphthalene, diphenyloxide, etc. is led into the vessel through 29 and reacted with the fluorine dispersed through it by a spray forming arrangement 28.

A suitable solvent or liquid reaction medium such as carbon tetrachloride, or the -like may be introduced with the raw material in order'to decrease the violence of the reaction. An inert 400' E, unsaturated hydrocarbons, unsaturated glycerides. drying oils, oxygenated compounds. etc. is to lead the 1-D? gas from 3 directlyinto the fluorinator 26 through line 35. This is also a. means. of stabilizing unstable organic compounds. Heat may also be used, as tor example temperatures 01' 40 F., 100 F., 200. F.,' 450' 1".,

4 or even 500 FQwith or without theuse of superatmospheric pressure. In such cases it is generally desirable to carry out the reaction in presence of a fluorination catalyst such as iodlne,'and the like, or a metal halide or'metal fluoride as for gas or vapor such as nitrogen, carbon dioxide, and

the like may also be introduced with the fluorine (from 10 to 90% of the total mixture) through line 36 to assist in the same manner. It is sometimes advantageous to introduce chlorine, hy-

drogen chloride, hydrogen fluoride or other halogen or halogen compounds with the fluorine. Jinv HF formed in the reaction may be bled oil at 3| and collected or introduced at some point in line 4 such as 34 for recovery. In the case of very reactive compounds such as naphthalene and many other organic compounds, it. is necessary example bromine, antimony trichloride, anti-- mony pentafluoride, and the like, may likewise be present.

Another alternative method which may be em ployed with raw materials reactive with HF, as

chlorinated organic compounds boiling ab ve example antimony penta or tri-chloride, bismuth trichloride, boron trifluoride, etc. For example, chlorinated castor oil or chlorinated wax may be introduced into the fluorinator at 29. together with some antimony chloride ("say $5 to 20% by weight), and reacted with HF entering-at. 22. A solventsuch as kerosene, naphtha. white oil, or cyclohexane may be added with the charge. After the reaction has progressed to the desired stage, the products may be drawn 01! at 21, or they may be drawn oil. continuously while a continuous stream of raw material is red in. In many cases it is not necessary to replace all of the chlorine in the material treated, and the resulting chloro-fluoro compound can be employed for a variety or purposes. Sometimes the products are suitable even when only very small quantities of fluorine are present.

The materials produced according to this invention may be employed as blending agents in lubricants, as for example as extremepressure lubricants or flre resisting lubricants, and they may be used as such, without diluents, for the preparation of lubricating oils, turbine oils, greases, and the like. For example, a blend of 5 to or more of a fluoro compound in a mineral, synthetic or glyceride oil is satisfactory for reducing the lnflammability, while 0.01 to 5% of the fluoro or fluoro-chloro compound may be used as an oxidation or polymerization inhibitor, or as a blending agent to improve the oil in other respects. The products, such as those containing between 5 to fluorine or more, may also be employed as coatings, impregnating materials fornbrous substances as wood, cloth, andthelike, as ingredients in paints, varnishes, lacquers and enamels.

Due to their stability and combustion resistant leum hydrocarbons, as precipitating agents, and

as non-igniting oils for lubrication. insulation, for use in transformers, cables, condensers, and other similar purposes, especially when they contain from approximately 10 to 60% fluorine. Plastic compositions containing 5 or 10 to 60% of such fluorinated organic compounds are very suitable as moulding materials for various articles i of furniture, equipment, etc. Resins may be fluorinated, especially when dissolved in solvents or admixed with other ingredients so as to contain 5 to 50% fluorine or even more. Various other materials such as paper, wood, cloth, leather, and the like may be treated with fluorine to improve the qualities thereof.

described may also be employed to advantage as raw materials for chemical syntheses. For example, they may be condensed with aromatic hydrocarbons, other aromatic compounds, halogenated compounds, and the like, to yield excellent blending agents for lubricants or fuels. They may also be reacted with materials of the sodium polysulfide type to yield useful plastics and oils. Numerous other condensation, polymerization,

defiuorination, and addition reactions may be Iclaim:

1. An impregnating and plasticizing composition comprising a fluorinated organic compound boiling above 400 F., in which the fiuorinated organic compound contains from 5 to 60% cf 2. An. impregnated fibrous material containing a non-inflammable fluorinated organic compound boiling above 400 F., in which the fluorinated organic compound contains from 5 to 60% of fluorine. i

3. A plastic composition comprising about 10- 60% of a fiuorinated organic compound boiling above 400 F.

4. A plastic composition according to claim 3 in the form of a film coating.

PETER J GAYLOR. 

